Metal oxide films are useful in a variety of applications in the semiconductor industry such as, for example, lithographic hard masks, underlayers for anti-reflective coatings and electro-optical devices. For example, photoresist compositions are used in microlithography processes for making miniaturized electronic components, such as in the fabrication of computer chips and integrated circuits. Generally, a thin coating of a photoresist composition is applied to a substrate, such as a silicon-based wafer used for making integrated circuits. The coated substrate is then baked to remove a desired amount of solvent from the photoresist. The baked, coated surface of the substrate is then image-wise exposed to actinic radiation, such as visible, ultraviolet, extreme ultraviolet, electron beam, particle beam or X-ray radiation. The radiation causes a chemical transformation in the exposed areas of the photoresist. The exposed coating is treated with a developer solution to dissolve and remove either the radiation-exposed or the unexposed areas of the photoresist.
The trend towards the miniaturization of semiconductor devices has led to the use of new photoresists that are sensitive to shorter and shorter wavelengths of radiation and has also led to the use of sophisticated multilevel systems to overcome difficulties associated with such miniaturization.
Absorbing antireflective coatings and underlayers in photolithography are used to diminish problems that result from radiation that reflects from substrates which often are highly reflective. Reflected radiation results in thin film interference effects and reflective notching. Thin film interference, or standing waves, result in changes in critical line width dimensions caused by variations in the total light intensity in the photoresist film as the thickness of the photoresist changes. Interference of reflected and incident exposure radiation can cause standing wave effects that distort the uniformity of the radiation through the thickness. Reflective notching becomes severe as the photoresist is patterned over reflective substrates containing topographical features, which scatter light through the photoresist film, leading to line width variations and, in extreme cases, forming regions with complete loss of desired dimensions. An antireflective coating film coated beneath a photoresist and above a reflective substrate provides significant improvement in lithographic performance of the photoresist. Typically, the bottom antireflective coating is applied on the substrate and cured, followed by application of a layer of photoresist. The photoresist is imagewise exposed and developed. The antireflective coating in the exposed area is then typically dry etched using various etching gases, and the photoresist pattern is thus transferred to the substrate.
Underlayers containing high amount of refractory elements can be used as hard masks as well as antireflective coatings. Hard masks are useful when the overlying photoresist is not capable of providing high enough resistance to dry etching that is used to transfer the image into the underlying semiconductor substrate. In such circumstances, a hard mask whose etch resistance is high enough to transfer any patterns created over it into the underlying semiconductor substrate can be employed. This is possible when the organic photoresist is different enough from the underlying hard mask so that an etch gas mixture can be found which will allow the transfer of the image in the photoresist into the underlying hard mask. This patterned hard mask can then be used with appropriate etch conditions and gas mixtures to transfer the image from the hard mask into the semiconductor substrate, a task which the photoresist by itself with a single etch process could not have accomplished.
Multiple antireflective layers and underlayers are being used in new lithographic techniques. In cases where the photoresist does not provide sufficient dry etch resistance, underlayers and/or antireflective coatings for the photoresist that act as a hard mask and are highly etch resistant during substrate etching are preferred. One approach has been to incorporate silicon, titanium, zirconium or other metallic materials into a layer beneath the organic photoresist layer. Additionally, another high carbon content antireflective or mask layer may be placed beneath the metal containing antireflective layer, to create a trilayer of high carbon film/hard mask film/photoresist. Such trilayers can be used to improve the lithographic performance of the imaging process.
Conventional hard masks can be applied by chemical vapor deposition, such as sputtering. However, the relative simplicity of spin coating versus the aforementioned conventional approaches makes the development of a new spin-on hard mask or antireflective coating with high concentration of metallic materials in the film very desirable.
Underlayer compositions for semiconductor applications containing metal oxides have been shown to provide dry etch resistance as well as antireflective properties. When higher concentrations of metal oxide are present in the underlayer, improved etch resistance and thermal conductance can be achieved. Conventional metal oxide compositions, however, have been found to be very unstable to moisture in air creating a variety of issues, including shelf life stability, coating problems and performance shortcomings. As well, conventional compositions generally contain non-metal oxide materials such as polymers, crosslinkers and other materials that detract from the metal oxide properties required for etch resistance and thermal conductivity. Thus, there is an outstanding need to prepare spin-on hard mask, antireflective and other underlayers that contain high levels of stable soluble metal oxides which are soluble or colloidally stable. It would be advantageous to provide such layers that have a high metal content. In addition, it would be advantageous to provide such layers that have excellent moisture resistance. Further, it would be advantageous to provide such layers with improved etch selectivity to SiOx with CF4 or oxygen gas.